Dyeing human hair with an oxidation dye and 1-phenyl-3-methyl-5-pyrazolone



Nov. 26, 1968 0 i/ca/ Density in Degrees Verne G. GHILARDI ETAL DYEING HUMAN HAIR WITH AN OXIDATION DYE AND l-PHENYL--METHYL-5PYRAZOLONE Filed Jan. 28, 1965 fin/en fors G. vi/ardi :7. R Zemonnier' United States Patent 3,413,072 DYEING HUMAN HAIR WITH AN OXIDA- TION DYE AND 1-PI-IENYL-3-METHYL-5- PYRAZOLONE Giuliana Ghilardi and Jacqueline Raymonde Lemonnier, born Richard, Paris, France, assignors to Societe Anonyme dite: LOreal, Paris, France Filed Jan. 28, 1965, Ser. No. 428,701 Claims priority, application France, Feb. 4, 1964, 962,624 5 Claims. (Cl. 811) ABSTRACT OF THE DISCLOSURE A process for dyeing human hair with an oxidation dye, which comprises dyeing the hair with a composition containing an effective amount of the dye, an oxidation retarding amount of 1-phenyl-3-methyl-5-pyrazolone and an effective amount of an effective oxidizing agent.

This invention relates to the dyeing of hair using oxidation dyes, and in particular the use of 5-pyrazolones as oxidation retarders.

Most hair dyeing processes use so-called oxidation dyes, that is, dyes which must be brought into contact with an oxidising agent before they can have a dyeing effect, the oxidising agent, for instance hydrogen peroxide, causing components of the oxidation dye to couple together. The oxidising agent can also serve, where necessary, to decolorise the hair partially so as to obtain at the end of the dyeing process a coloration which is lighter than the initial coloration.

Since oxidation dyes are extremely sensitive to oxidising agents, it is generally necessary to protect the dyes against accidental oxidation during storage and to control their oxidation during the hair dyeing.

It is essential that at the time of use, when the oxidation dye is mixed with the oxidising agent, the oxidative coupling of the dye should be delayed to a suflicient extent that it takes place after the product has been applied to the hair and not in the vessel in which the mixing has taken place. This requirement is of great importance in practice, because when oxidation takes place in the mixing vessel the dyeing power of the mixture gradually decreases, and it becomes impossible to obtain levelness, ie the same coloration of all the locks of one head of hair if, between the time when the dyeing composition has been applied to the first lock and the time when it has been applied to the lock last treated, the mixture being applied to the hair has become substantially oxidised.

Apart from the weakened shade obtained with a partially oxidised composition, the fastness of this weakened shade is much lower than that of the coloration obtained with the aid of a dyeing composition which has just been freshly prepared by mixing of the dye and of the oxidising agent. Moreover, the appearance of a dye which oxidises too quickly is quite unattractive and the consequent rapid darkening makes it impossible to follow the taking of the dye.

Attempts have been made to retard the oxidation of the oxidation dyes, and proposals have been made for using substances such as ammonium thioglycollate, sodium sulphite or ascorbic acid, which have the effect of delaying to some extent the oxidative coupling of the dyes. However, the delaying action exerted on the coupling by the use of such compounds has been found in practice to be insufiicient, the dyeing compositions suffering an appreciable darkening before all the locks of hair can be treated.

Patented Nov. 26, 1968 We have now found according to the present invention that 5-pyrazolones, especially 1-phenyl-3-methyl-5-pyrazolone, can exert a satisfactory retarding effect upon the oxidative coupling of oxidation dyes. Thus, the present invention consists in one aspect of compositions suitable for use in dyeing hair, especially human hair, comprising an oxidation dye and a 5-pyrazolone as an oxidation retarder for the dye.

The present invention also consists in a process for dyeing human hair with an oxidation dye, which comprises mixing the dye with a S-pyrazolone and with an oxidising agent, the S-pyrazolone being mixed with the dye not substantially later than the mixing together of the dye and the oxidising agent, applying the mixture to the hair, allowing suflicient time to elapse for the dye to exert its dyeing effect and then removing any unwanted excess of the mixture or its components from the hair. i

In this specification and its claims the term oxidative dye is used to refer to either the dyestuff used to dye the hair or to its precursor prior to admixture with the oxidising agent, and the appropriate meaning is to be understood in accordance with the context,

The amount of S-pyrazolone in the compositions and process of this invention is preferably 1 to 50 moles of S-pyrazolone per moles of oxidation dye. In order to improve the stability of the compositions of the invention they can contain a preservative, for instance ammonium thioglycollate, sodium sulphite or ascorbic acid.

The invention is illustrated by the following examples.

EXAMPLE 1 A composition of the invention is prepared by mixing the following:

Condensation product of 1 mol of nonylphenol and 4 mols of ethylene oxide -g 270 Condensate of 1 mol of nonylphenol and 9 molecules of ethylene oxide g 230 Ethyl alcohol g 160 Ammonia (22 B.) cc p-Toluylenediamine g 14 m-Diaminoanisole g 0.5 Resorcinol g 6 m-Aminophenol g 2.2 p-Aminophenol g 2.3 1-phenyl-3-methyl-5-pyrazolone g 7 Ethylenediaminetetracetic acid g 2 Water q.s. for 1000 g.

This composition is mixed just before use with an equal volume of hydrogen peroxide (20 vol.), the mixture thus obtained forming a transparent red gel which can be kept for about 30 minutes without undergoing any appreciable change. When applied to 90% white hair, by the usual method it gives, after rinsing and drying, a light-brown shade.

EXAMPLE 2 A composition according to the invention is prepared by mixing:

Oleic acid g Condensate of 1 mol of synthetic oxo alcohol and 3 molecules of ethylene oxide g 250 Butyl Cellosolve g 50 Ethyl alcohol g 150 Ammonia (22 B.) cc 100 p-Toluylenediamine g 13 .5 m-Diarninoanisole -g-.. 0.5 Resorcinol g 5 3 p-Aminophenol =g 2.3 1-phenyl-3-methyl-5-pyrazolone g 7 Diethylenetriaminepentacetic acid (sodium salt) g 2.

Water q.s. for 1000 g.

This composition is mixed just before use with an equal volume of hydrogen peroxide (20 vol.), the mixture thus obtained forming a transparent red gel which can be kept for about 30 minutes without undergoing any appreciable change. When applied to 90% white hair by the usual method, it gives, after rinsing and dry ing, a light-brown shade.

The effect as oxidation retarder of 1-phenyl-3-methyl- S-pyrazolone has been compared with oxidation retarder of the prior art in the following tests. Six test solutions were prepared having the compositions shown below. Solutions 2, 3 and 4 contained oxidation retarders of the prior art, Solutions 5 and 6 contained 1-phenyl-3- methyl-S-pyrazolone as oxidation retarder and Solution 1 was a control containing no oxidation retarder.

Solution 1 p-Toluylenediamine base mole 0.01 Ethylenediaminetetracetic acid g 0.1 Ammonia (20%) cc 10 Water q.s. for 100 g.

Solution 2 p-Toluylenediamine base mole 0.01 Ethylenediaminetetracetic acid g 0.1 Ammonia (20%) cc 10 Ascorbic acid (0.001 mole) g 0.176 Sodium hydroxyde (0.002 mole) g 0.08 Water q.s. for 100 g.

Solution 3 p-Toluylenediamine base mole 0.0] Ethylenediaminetetracetic acid g 0.1 Ammonia (20%) cc 10 Ammonium thioglycollate (0.001 mole) 'g 0.095 Water q.s. for 100 g.

Solution 4 p-Toluylenediamine base mole 0.01 Ethylenediaminetetracetic acid g 0.1 Ammonia (20%) cc 10 Sodium sulphite (0.001 mole) g 0.126 Water q.s. for 100 g.

Solution 5 p-Toluylenediamine base mole 0.0] Ethylenediaminetetracetic acid g 0.1 Ammonia (20%) cc 10 1-phenyl-3-methyI-S-pyrazolone (0.001 mole) g 0.174 Water q.s. for 100 g.

1-phenyl-3-methyl-5-pyrazolone (0.002 mole) g 0.348 Water q.s. for 100 g.

Before each experience, each of these solutions was mixed an equal weight of hydrogen peroxide (30 vol.),

Solution Absorption (optical density/100) (degrees Verne) Time (mins):

0 6 2. 5 7. 8 4. 9 2. 2 2. 2 10. 7 8. 5 11. 4 10. 6 3. 3 2. l 15. 1 15. 5 16.4 14. l 4. 6 l. 5 22 21. 6 23. 9 20. 1. 8. 8 2. 1 27. 4 27. 7 27. 2 22. 1 12. 7 2. 7 39. 6 36. 7 33. 5 28. 3 20. 3 4. 4

The results obtained are reproduced on the accompanying drawing in which the optical density (expressed in degrees Verne) has been plotted against time in minutes. The number against each curve corresponds to the number of the test solution.

It will be noted that, especially during the period up to 30 minutes after mixing, which corresponds to the time commonly taken to apply a dye composition to the head, the 1-phenyl-3-methyl-5-pyrazolone shows substantially no increase in optical density.

What we claim is:

1. A process for dyeing human hair with an oxidation dye which comprises dyeing the hair with a composition containing an effective amount of the dye, an oxidation retarding amount of 1-phenyl-3-methyl-5-pyrazolone and an effective amount of an oxidizing agent.

2. The process of claim 1, in which the 1-phenyl-3- methyl-S-pyrazolone is in an amount of 150 mols per 100 mols of oxidation dye.

3. The process of claim 1, wherein oxidative coupling of the dye takes place after the dye has been applied to the hair.

4. The process of claim 1, wherein said oxidizing agent is hydrogen peroxide.

5. The process of claim 1, wherein said composition also contains a preservative selected from the group consisting of ammonium thioglycollate, sodium sulphite and ascorbic acid.

References Cited UNITED STATES PATENTS 1,019,576 3/1912 Wolffenstein et al. 167-88 2,186,849 1/1940 Wilmanns et al. 6 X 2,294,909 9/1942 Jennings 2603l0 X 2,311,082 2/1943 Porter et a1. 260-310 X 2,610,941 9/1952 Schueller 16788 3,062,650 11/1962 Sagura et al 96-90 OTHER REFERENCES Chemical Abstracts, vol. 43, p. 6846b (1949). Chemical Abstracts, vol. 47, 12065-12066 (1953).

! ALBERT T. MEYERS, Primary Examiner.

V. C. CLARKE, Assistant Examiner. 

